Synthesis, structures and electrochemical properties of amino-derivatives of diiron azadithiolates as active site models of Fe-only hydrogenase

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• 作者：Weiming Gao ; Jianhui Liu ; Chengbing Ma ; Linhong Weng ; Kun Jin ; Changneng Chen ; Bjö ; rn //www.sciencedirect.com/scidirimg/entities/212b.gif" alt="Angstrom capital A ; ring" border=0>ke
• 关键词：Bioinorganic chemistry ; Catalysis ; Hydrogen production ; Iron– ; sulfur complex
• 刊名：Inorganica Chimica Acta
• 出版年：2006
• 期刊代码：40_00201693
• 类别：ch
• 出版时间：1 March 2006
• 卷：359
• 期：4
• 页码：1071-1080
• 文件大小：440 K

摘要

The preparation and characterization of two novel amino-incorporated sulfur-bridged dinuclear iron (I) complexes of the type [NR(μ-SCH<sub>2sub>)<sub>2sub>]Fe<sub>2sub>(CO)<sub>6sub>, one being amino protected [N(CH<sub>2sub>CH<sub>2sub>NHTs)(μ-SCH<sub>2sub>)<sub>2sub>]Fe<sub>2sub>(CO)<sub>6sub> (8) and the other [(μ- SCH<sub>2sub>)<sub>2sub>Fe<sub>2sub>(CO)<sub>6sub>NCH<sub>2sub>CH<sub>2sub>N (μ-SCH<sub>2sub>)<sub>2sub>]Fe<sub>2sub>(CO)<sub>6sub> (9) are described. These two complexes are readily prepared in a S<sub>Nsub>2 manner between double lithium anion and bis(chloromethyl) amine derivatives. The structures of 8 and 9 were characterized by IR, ¹H, ¹³C NMR, MS and HRMS spectra and further determined by X-ray analyses. Protonation of complex 8 gave the mono N-protonated product, while for 9 the protonation occurred in both of the N atoms. The redox properties were evaluated by cyclic voltammograms. It was shown that these two complexes can catalyze electrochemical reduction of proton to molecular hydrogen.